Zinc silicate phosphor



Oct. 20, 1953 R. NAGY ET AL ZINC SILICATE PHOSPHOR Filed May l2, 1948 INVENTORS Papal/0H A/H'y Jan/.Waufwr/N.

BY mum I ATTORNEY Patented Oct. 20, 1953 flumrreo rA'rEfs param ZINC: Y Rudolph' .Nagy-` and Robert W..Wo1lentin,.loom

felc l,"l\l.` J. ,;.assig`nors to Westinghouse IElectric Corporation, -East Pittsburgh, 1 Pa., a corporationof Pennsylvania wpplieaton -Mayv12, 1948, Serial No. 26,488

This` invention relatelto. phosphoreandmethfoils Qfmakhg, and ymore.,particularlyto .a .Zine

silicate phosphor" heu/.ing .increased -eiiieieney .and improved maintenance.

"The principal object. epur inventionleeneralily .consideredy .is to produoe a hieheou.tpptzino` .Sili- .eate phosphor pv .activation .with ,magnesium and/or zirconium .andmanganesa Another object vof ,oprlinventon .is to. produce a'rnallganeseactivated zinc magnesium silicate .,phosphor.

A 4further i obj ect of gourdinvention is to produce ai manganesefaetivated .zine zirconium silicate phosphor.

'Other objectsand advantages ofthe invention .l ;will*become' apparent as the description proceeds.

Reierringf'to the idrawing, Figure NV1 is' an elevationalview, `with a part in y longitudinal section, of Va ,fluorescent lamp. embodying ourinvention. n

lFigurez lis a 'flow diagram' illustrating embodianentsof our-method.

' 'The ,usual 4method of .preparing zinc silicate phosphor for fluorescent'lampsis .to mix zinc oxide and silicio acid ina ratio ofv aboutl'Z to 1;0 `v-rnolefadd abouti-1% ofema-nganese'in the form -oft-he carbonate,` and heat atatemperature'of aboutl2-80 C. v'rl-'piu'lsphor so produced and incorporated in a 40 watt fluorescent lamoasan -1jexample,- initially gives=an output 'of about `90 l vlumens-per Watt, -and afterilOO hours-,burning the output has dropped to about'jlumensper 'Inaaecordanoe' with lour -invention'to lbe 4now vLdeseribed;we have ubeen ableu to initially obtain 'a02-.6j lumens {per-v Watt and '90.9' lumens per -Watt after 100 f hoursfburning, Iwith i a lamp as illustrated in Figure 1. It will thus be seen that `we not only initially obtainlincreased output, but

theemaintenanceloflampslusing our new phos- 1 phor is improved.

iefpreierred methpdof preparineecur :phosphor is to use magnesium as an activator, along with manganese, in aazince-silicate Whichfmay be consideredias approxmatingthe ortho-silicate, was :distinguished .fromthe .former-...silicateapproxi- ,imating theametasilicate. y:However it is desirable :i-rtofthave .aslight excessoi si 'cc acid overathe itheoretieallzinc,ortho-.Silieate .ZnzSiOs- 1..Affpreferred formula is approximately as follows:

1.8 moles zinc oxide (phosphor grade) 1.0 mole silicio acid (phosphor grade) .078 mole manganese (preferably as the carbonate which may be expressed as 2% by Weight) .0135 mole magnesium (preferably as the nitrate) The ingredients are desirably ball-milled together for one hour with a small amount of distilled water, dehydrated at about 130 C., and then heated at about 12401 C. for about onehour. .They are` then put through. adesirably. :.100 mesh .,screen,.and. rered for. from `,one Y,toithree hours, as represented `in Eigure?, until there is no. .Change inthe .output as.determined.pymeasuring a small plaque ofthe phosphor.

The mole. pr,opsnrtionl of tnernaeneeium ,sa1t...ifh

. .the silicatelwniehmaxbe the nitrata-oarbonate, `hydroxide,any known Ycompound..readily-scie.earnposable to the oxide, or the oxide itsel;f, .anbe

-. varied. between .thelixnits .of .00.5 mole and .10

mole, for .monofmasnesium compounds, and

varied` if other vconripoundsare employed, to.. give e ,corresponding ,proportions `of magnesium within the scope of our invention. However,.yvfe2 prefer .to use .the .mo1epropnrtion; given in the. above formula. .or one .within t lle-optimum range. between .012and .015,imQ1e. ',Instead of,niangar,rese carbonate, can uselthelsilioatewan ,oxidenor .anyflrnown ,manganese eompound readily decompoeable to. 4the .oxidein .mole.proportientogite` sa -corresponding amount .of manganese;

"AS an. alternative, we may activate` zinogsilieate by zirconium, as Well as manganese, usingthe l .Sameproeedure `.as-formaglie.Si-1.1m,. except that desirablynabout ,.02. imple of zlcOhium YOXClefare used inplace ofthe magnesium salt. ,Y'Ihe lrange of concentration 4offzircorlllln Compounds, .in Which deSredtaetil/atonlcan :be obtained, ispetween ..005 eand2.11.1ole. .Withsuch a formula,

.We have .initially obtainedla lnmensper .Watt using zirconium as an aetiratonand .lumens per Watt .after burning ,10.0 hours, Whielris oon- .'Siderably better thantheregu1-armanaanesefactiv ated z irrc, silicate.

4ne a Jvhird alternative, l.we.mayaetiratewith both. magnesium and .zreoniuraaslwell as manganese.. Within tnelirnits ...005. to ..10. inoleof the magnesiumand.Zireoniurn.ingredients aggregated 1in any` proportion,..in aeeordanee With the-,flow I'diagram ,Ofiigllrei 2. .A .typical iormula would thus be approximately as follows:

vlamoles:zineeoxide `(phosphor grade) i110 uncle silicio acid (phosphor grade) 2:0.'78 mole manganese (preferably asthe carbonate which I,may Ybe. expressed as l21% Ybyaiveight) Between-$0.5 and ,-:10y mole-magnesium :(:prefer- .ably .as the..nitrateamixedinfanr prpportonwith 3 improved stability. Although preferred embodiments of our invention have been disclosed, it will be understood that modifications may be made within the spirit and scope of the appended claims.

We claim:

1. A manganese-activated zinc silicate phosphor for iiuorescent lamps additionally activated by one of the elements selected from the group consisting of magnesium and zirconium in mole proportions about .005 to .10 and about .005 to .20, respectively.

2. A manganese-activated zinc silicate phosphor for uorescent lamps additionally activated by between about .005 and .10 mole of magnesium.

3. A manganese-activated zinc silicate phosphor for fluorescent lamps additionally activated by between about .O05 and .20 mole of zirconium.

4. A manganese-activated zinc silicate phosphor for fluorescent lamps additionally activated by one of the elements selected from the group consisting of magnesium and zirconium in mole proportions about .012 to .015 and about .02, respectively.

5. A zinc silicate phosphor for uorescent lamps, approximating the orthosilicate, and activated per mole by between about .012 and .015 mole of magnesium and about .078 mole of manganese.

6. A zinc silicate phosphor for iiuorescent lamps, approximating the orthosilicate, and activated per mole by about .0135 mole of magnesium and about .078 mole of manganese.

7. A zinc silicate phosphor for fluorescent lamps, approximating the orthosilicate, and activated per mole by between about .005 and .2 mole of zirconium, and about .078 mole manganese.

8. A zinc silicate phosphor for iiuorescent lamps, approximating the orthosilicate, and activated per mole by about .02 mole of zirconium and about .078 mole of manganese.

9. A phosphor for fluorescent lamps comprising the red reaction product of the following raw material constituents in about the stated proportions: zinc oxide, 1.8 moles; silicio acid, 1.0 mole; a magnesium compound such as the oxide, or decomposable thereto, and equivalent in magnesium content to .0135 mole of the nitrate; and manganese, .078 mole.

10. A phosphor for fluorescent lamps comprising the fired reaction product of the following raw material constituents in about the stated proportions: zinc oxide, 1.78 moles; silicic acid, 1.0 mole; zirconium oxide, .02 mole; and manganese, .078 mole.

11. The method of making a zinc silicate phosphor having increased efciency and improved maintenance, comprising grinding together zinc oxide, silicio acid, manganese carbonate, and magnesium nitrate with a small amount of distilled water for about one hour, drying at about 130 C., firing at about 1240 C. for about one hour, sieving through a preferably mesh screen, and rering at about 1240" C. for from one to three hours.

12. The method of making a zinc silicate phosphor having increased efficiency and improved maintenance, comprising grinding together zinc oxide, silicio acid, manganous carbonate, and zirconium oxide with a small amount of distilled water for about one hour, drying at about C., ring at about 1240 C. for about one hour, sieving through a preferably 100 mesh screen, and reni-ing at about 1240 C. for from one to three hours.

13. The method of making a zinc silicate phosphor having increased eii'iciency and an improved maintenance, comprising grinding together zinc oxide, silicic acid, manganese carbonate, zirconium oxide, and magnesium nitrate with a small amount of distilled water for about one hour, drying at about 130 C., ring at about 1240 C. for about one hour, sieving through a preferably 100 mesh screen, and reiiring at about 1240 C. for from one to three hours.

14. The method of making a zinc silicate phosphor having increased efliciency and improved maintenance comprising grinding together zinc oxide, silicio acid, manganese carbonate, and at least one of the materials selected from the group consisting of magnesium nitrate and zirconium oxide for about two hours, firing at about 1240" C'. for about one hour, sieving through -a preferably 100 mesh screen, and rering at about 1240 C. for from one to three hours.

15. A zinc silicate phosphor for iiuorescent lamps activated by about .078 mole of manganese and one of the elements selected from the group consisting of magnesium and zirconium in mole proportions about .005 to .10 and about .005 to .20, respectively.

16. A zinc silicate phosphor for iiuorescent lamps activated by about .078 mole of manganese and between about .005 and .10 mole of magneslum.

17. A zinc silicate phosphor for fluorescent lamps activated by manganese and about .0-2 mole of zirconium.

18. A zinc silicate phosphor for fluorescent lamps activated by about .078 mole of manganese and one of the elements selected from the group consisting of magnesium and zirconium in mole proportions about .012 to .015 and about .02. respectively.

RUDOLPH NAGY. ROBERT W. WOLLENTIN.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,103,085 McKeag Dec. 21, 1937 2,212,209 Leverenz Aug. 20, 1940 2,314,699 Hale Mar. 23, 1943 2,447,448 Williams Aug. 17, 1948 

1. A MANGANESE-ACTIVATED ZINC SILICATE PHOSPHOR FOR FLUORESCENT LAMPS ADDITIONALLY ACTIVATED BY ONE OF THE ELEMENTS SELECTED FROM THE GROUP CONSISTING OF MAGNESIUM AND ZIRCONIUM IN MOLE PROPORTIONS ABOUT .005 TO 10 AND ABOUT .005 TO .20, RESPECTIVELY. 